The invention concerns water-soluble and water-dispersible monomers and resins and processes for preparing aqueous resin compositions.
Aqueous resin compositions are widely used in many different fields, including coatings, inks, detergents, additives for plastics, water treatment, papermaking, and oil field production and refining. In particular, polyacrylamide and copolymers of acrylamide have gained prominence as nonionic or cationic polymers that are water soluble. Because of industrial hygiene considerations associated with use of acrylamide monomer, a replacement for acrylamide has long been sought. Modifications such as N-substituted acrylamide monomers (e.g., N-methylol acrylamide) have been proposed. Polymers produced with the acrylamide and modified acrylamide monomers, however, have other shortcomings that make them undesirable. For example, the only reactive functional group of acrylamide is the unsaturation, so the polymerized acrylamide unit does not provide a site for crosslinking or further modification. Crosslinking or other modification of the acrylamide unit would be useful to reduce water sensitivity of the homopolymer or copolymer at an appropriate time.
Thus it would be desirable to provide a water soluble monomer that could be used in the place of acrylamide, would not have the industrial hygiene concerns associated with acrylamide, and could be modified when it would be appropriate to reduce the water sensitivity of a polymer prepared from the water soluble monomer.
We have now invented a method of preparing improved aqueous resin compositions. The resins are prepared by employing a xcex2-hydroxy carbamate monomer. The xcex2-hydroxy carbamate monomer is polymerized to form water-soluble homopolymers or, if polymerized as a mixture with one or more comonomers, copolymers that are soluble or dispersible in water. The xcex2-hydroxy carbamate monomer of the invention can be used as a replacement for acrylamide, especially for preparing aqueous resin compositions. The xcex2-hydroxy carbamate monomer offers an advantage of providing reactive sites for crosslinking or other reactions after polymerization.
When used in connection with the invention, the term xe2x80x9ccarbamate groupxe2x80x9d refers to a group having a structure 
in which R1 is H or alkyl. Preferably, R1 is H or alkyl of from 1 to about 4 carbon atoms, and more preferably R1 is H.
When polymerized, the monomer of the invention provides two reactive sites, a hydroxyl group and a reactive carbamate group, for crosslinking or other modification of the polymer.
The xcex2-hydroxy carbamate monomer has an ethylenically unsaturated group and a xcex2-hydroxy carbamate group. Preferably, there are from 1 to about 4 carbons between the ethylenically unsaturated group and the xcex2-hydroxy carbamate group. The xcex2-hydroxy carbamate monomer of the invention can be represented by a structure: 
wherein either each R2 is hydrogen or one R2 is hydrogen and the other R2 is methyl; n is from 1 to about 4, preferably 1; and one of Y and Z is OH and the other of Y and Z is 
wherein R1 is H or alkyl. Preferably, R1 is H or alkyl of from 1 to about 4 carbon atoms, and more preferably R1 is H. In a typical synthesis of the xcex2-hydroxy carbamate monomer, the reaction kinetics produces a product that is a mixture of the compound in which Y is hydroxyl and Z is the carbamate group and the compound in which Z is a hydroxyl and Y is the carbamate group.
Unlike acrylonitrile, the monomer of the present invention has reaction rates comparable to other acrylic monomers. The monomer can be polymerized to form a homopolymer. The polymerization can be carried out in water or in an a mixture that includes water. The monomer of the invention can also be copolymerized with other monomers, including acrylic, methacrylic, vinylic and allylic monomers, again preferably in an aqueous medium. Particular examples of suitable comonomers include, without limitation, acrylic acid, methacrylic acid, crotonic acid, esters of these acids, maleic anhydride, styrene, alpha-methylstyrene, vinyl acetate, and so on. Other functional monomers may be copolymerized along with the xcex2-hydroxy carbamate monomer, including, without limitation, acid- and anhydride-functional monomers such as those already mentioned; hydroxyl-functional monomers such as hydroxyalkyl acrylates and methacrylates, amino-functional acrylic monomers such as t-butylaminoethyl methacrylate and t-butylamino-ethylacrylate; epoxide-functional monomers such as glycidyl acrylate, glycidyl methacrylate, and allyl glycidyl ether; other carbamate-functional monomers, and so on.
One way of preparing the xcex2-hydroxy carbamate monomer of the invention is by reacting a glycidyl-group containing polymerizable monomer first with carbon dioxide to convert the oxirane group to a cyclic carbonate group, and then with ammonia or a primary amine to convert the cyclic carbonate group to a xcex2-hydroxy carbamate group. Examples of suitable oxirane group-containing polymerizable monomers include, without limitation, glycidyl acrylate, glycidyl methacrylate, glycidyl crotonate, and allyl glycidyl ether. Oxirane groups can be converted to carbamate groups by first converting to a cyclic carbonate group by reaction with CO2. This can be done at any pressure from atmospheric up to supercritical CO2 pressures, but is preferably under elevated pressure (e.g., 60-150 psi). The temperature for this reaction is preferably 60-150xc2x0 C. Useful catalysts include any that activate an oxirane ring, such as tertiary amine or quaternary salts (e.g., tetramethyl ammonium bromide), combinations of complex organotin halides and alkyl phosphonium halides (e.g., (CH3)3SnI, Bu4SnI, Bu4PI, and (CH3)4PI), potassium salts (e.g., K2CO3, KI) preferably in combination with crown ethers, tin octoate, calcium octoate, and the like.
The cyclic carbonate group is reacted with ammonia or a primary amine. The primary amine preferably has up to four carbons, e.g. methyl amine. Preferably, the cyclic carbonate is reacted with ammonia. The ammonia may be aqueous ammonia (i.e., NH4OH). The reaction ring-opens the cyclic carbonate to form a xcex2-hydroxy carbamate monomer according to the invention.
The xcex2-hydroxy carbamate monomer is water soluble. In one embodiment of the invention, the xcex2-hydroxy carbamate monomer is polymerized to form a homopolymer. The homopolymer is water-soluble. The xcex2-hydroxy carbamate monomer may be polymerized in the presence of free-radical initiators or with a redox initiator system. Useful initiators and redox initiator systems are well-known. The polymerization may be carried out without solvent or in an organic or aqueous medium. In a preferred embodiment, the xcex2-hydroxy carbamate monomer is polymerized in an aqueous medium, preferably without any organic solvent or with a minor amount (up to about 10% by weight of the aqueous medium) of a polar solvent such as methanol, tetrahydrofuran, propylene glycol monomethyl ether, or other water-soluble or water-miscible solvents. The xcex2-hydroxy carbamate monomer may be dissolved in water along with the initiating system and polymerized at a suitable temperature for the initiating system.
Alternatively, the xcex2-hydroxy carbamate monomer may be polymerized as a mixture with one or more comonomers. Depending on the comonomers chosen, and the ratio of the xcex2-hydroxy carbamate monomer with the other comonomers, the copolymers may be water soluble or water dispersible. As used herein, xe2x80x9cdispersiblexe2x80x9d or xe2x80x9cwater dispersiblexe2x80x9d encompasses not only dispersible (solid) copolymers, but also emulsifiable or water emulsifiable copolymers, that is, copolymers that are liquids or above their Tg at room temperatures and thus form emulsions. Examples of suitable comonomers include, without limitation, xcex1,xcex2-ethylenically unsaturated monocarboxylic acids containing 3 to 5 carbon atoms such as acrylic, methacrylic, and crotonic acids and the esters of those acids; xcex1,xcex2-ethylenically unsaturated dicarboxylic acids containing 4 to 6 carbon atoms and the anhydrides, monoesters, and diesters of those acids; vinyl esters, vinyl ethers, vinyl ketones, and aromatic or heterocyclic aliphatic vinyl compounds. Representative examples of suitable esters of acrylic, methacrylic, and crotonic acids include, without limitation, those esters from reaction with saturated aliphatic and cycloaliphatic alcohols containing 1 to 20 carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, 2-ethylhexyl, lauryl, stearyl, cyclohexyl, trimethylcyclohexyl, tetrahydrofurfuryl, stearyl, sulfoethyl, and isobornyl acrylates, methacrylates, and crotonates; and polyalkylene glycol acrylates and methacrylates. Representative examples of other ethylenically unsaturated polymerizable monomers include, without limitation, such compounds as fumaric, maleic, and itaconic anhydrides, monoesters, and diesters with alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, and tert-butanol. Representative examples of polymerization vinyl monomers include, without limitation, such compounds as vinyl acetate, vinyl propionate, vinyl ethers such as vinyl ethyl ether, vinyl and vinylidene halides, and vinyl ethyl ketone. Representative examples of aromatic or heterocyclic aliphatic vinyl compounds include, without limitation, such compounds as styrene, xcex1-methyl styrene, vinyl toluene, tert-butyl styrene, and 2-vinyl pyrrolidone. The comonomers may be used in any combination.
Aqueous solutions including the xcex2-hydroxy carbamate monomer may be polymerized in the presence of a free radical initiator at moderate temperatures, for example at temperature between about 20 and about 90xc2x0 C. When a copolymer is emulsion polymerized, the xcex2-hydroxy carbamate monomer is preferably used in an amount sufficient to stabilize the monomer emulsion during the polymerization process. Typically, the monomers may include from about 2 to 100 percent by weight, preferably from about 5 to 100 percent by weight, and more preferably from about 20 to 100 percent by weight, of the xcex2-hydroxy carbamate monomer.
Suitable free radical initiators include, without limitation, peroxide, persulfates, redox couples, azo compounds, and nonchemical means including ultrasound, UV light, ionizing radiation, and so on. Chain transfer agents may be included. Specific examples of useful initiators include, without limitation, hydrogen peroxide, ammonium persulfate, and redox systems, for example the combination of reducing species such as SO3xe2x88x92 with oxidants such as Fe+3 or the oxidation of thiourea by oxidants such as Fe+3. Specific examples of chain transfer agents include isopropanol, thiols such as octanethiol or mercaptoethanol, organohalides such as chloroform, diacetone alcohol, and the dimer of xcex1-methyl styrene.
The xcex2-hydroxy carbamate monomer can also be polymerized by other methods suitable for ethylenically unsaturated monomers. For example, without limitation, the xcex2-hydroxy carbamate monomer can be polymerized in an organic solvent, particularly a water miscible solvent. The homopolymer or copolymer of the xcex2-hydroxy carbamate monomer may then be diluted with water or inverted into water with or without distillation or stripping of the organic solvent. Methods for inversion of a water-soluble or water-dispersible polymer from an organic medium into an aqueous medium are known.
In an alternative embodiment, the homopolymer or copolymer including xcex2-hydroxy carbamate units may be prepared by including the corresponding cyclic carbonate monomer and forming the carbamate group from the carbonate group at some time during the polymerization of the corresponding cyclic carbonate monomer. For example, a primary amine or ammonia can be charged to the polymerization reactor and react with the cyclic carbonate group during the polymerization. The reactor can be pressurized for ammonia or a gaseous primary amine. The ammonia or primary amine could also be added during the polymerization reaction.
The homopolymers and copolymers of the xcex2-hydroxy carbamate monomer may have weight average molecular weights of from about 5000 to over a million. The most desirable weight average molecular weight will depend upon the use intended for the polymer. When the xcex2-hydroxy carbamate monomer is used as a replacement for acrylamide for a particular application, the amount of the xcex2-hydroxy carbamate monomer included and the preferred weight average molecular weight of the polymer prepared from it is comparable to the corresponding values for an acrylamide polymer for that application.
Homopolymers and copolymers of the xcex2-hydroxy carbamate monomer may be used in coating compositions, particularly waterborne coating compositions including topcoats. The homopolymers and copolymers of the xcex2-hydroxy carbamate monomer may also be used in other applications, especially in applications where acrylamide polymers have been used, including, without limitation, leather treatment, textile treatments, crop protection uses such as seed coatings, and in manufacture of fibers and inks. A homopolymer of the xcex2-hydroxy carbamate monomer may also be used as a dispersant or emulsifier for another polymer in preparing an aqueous composition. In particular, homopolymers or copolymers of the xcex2-hydroxy carbamate monomer may be used to incorporate hydrophobic resins and polymers into aqueous compositions. For example, the xcex2-hydroxy carbamate monomer may be used in the methods disclosed in Grandhee, U.S. Pat. Nos. 5,569,715 and 5,786,420 and Martin et al., U.S. Pat. No. 5,071,904, all three patents being incorporated herein by reference.
In one embodiment of the invention, the xcex2-hydroxy carbamate monomer is copolymerized with at least one monomer capable of forming a cationic group in water when salted. Examples of such cation-forming monomers include those having an aromatic group, preferably a quaternary ammonium salt obtained by the reaction of benzyl chloride and with an amino monomer such as dimethylaminoethyl (meth)acrylate, diethylaminoethyl(meth)acrylate, and dimethylaminohydroxylpropyl (meth)acrylate. The cationic copolymer is useful in water treatment, papermaking, oil field production and refining applications.
In another preferred embodiment, the homopolymers and copolymers of the xcex2-hydroxy carbamate monomer is used to prepare a coating composition. The coating composition preferably further includes a curing agent or crosslinker that is reactive with the one or both of the hydroxyl and carbamate functionalities of the xcex2-hydroxy carbamate monomer. The curing agent has, on average, at least about two reactive functional groups. The functional groups may be of more than one kind, each kind being reactive with one or both of the hydroxyl and carbamate groups.
Useful curing agents include materials having active methylol or methylalkoxy groups, such as aminoplast crosslinking agents or phenol/formaldehyde adducts; curing agents that have isocyanate groups, particularly blocked isocyanate curing agents, curing agents that have epoxide groups, amine groups, acid groups, siloxane groups, cyclic carbonate groups, and anhydride groups; and mixtures thereof. Examples of preferred curing agent compounds include, without limitation, melamine formaldehyde resin (including monomeric or polymeric melamine resin and partially or fully alkylated melamine resin), blocked or unblocked polyisocyanates (e.g., toluene diisocyanate, MDI, isophorone diisocyanate, hexamethylene diisocyanate, biurets, allophanates, and isocyanurates of these, which may be blocked for example with, e.g., alcohols, pyrazole compounds, or oximes), urea resins (e.g., methylol ureas such as urea formaldehyde resin, alkoxy ureas such as butylated urea formaldehyde resin), polyanhydrides (e.g., polysuccinic anhydride), and polysiloxanes (e.g., trimethoxy siloxane). Another suitable crosslinking agent is tris(alkoxy carbonylamino) triazine (available from Cytec Industries under the tradename TACT). The curing agent may be combinations of these, particularly combinations that include aminoplast crosslinking agents. Aminoplast resins such as melamine formaldehyde resins or urea formaldehyde resins are especially preferred. Combinations of tris(alkoxy carbonylamino) triazine with a melamine formaldehyde resin and/or a blocked isocyanate curing agent are likewise suitable and desirable. Component (b) may also contain groups that are reactive with the carbamate group of component (a), such as an acrylic polymer containing polymerized isobutoxymethyl acrylamide groups.
When monomers having a reactive group other than carbamate or hydroxyl are included in the copolymer, a crosslinker suitable for that reactive group may be included in the composition.
Although aqueous coating compositions that are free of regulated volatile organic compounds are preferred, a solvent may optionally be utilized in the coating composition used in the practice of the present invention. In general, the solvent can be any organic solvent and/or water. In one preferred embodiment, the solvent is a polar organic solvent. More preferably, the solvent is selected from polar aliphatic solvents or polar aromatic solvents. Still more preferably, the solvent is a ketone, ester, acetate, aprotic amide, aprotic sulfoxide, aprotic amine, or a combination of any of these. Examples of useful solvents include, without limitation, methyl ethyl ketone, methyl isobutyl ketone, m-amyl acetate, ethylene glycol butyl ether-acetate, propylene glycol monomethyl ether acetate, xylene, N-methylpyrrolidone, blends of aromatic hydrocarbons, and mixtures of these. In another preferred embodiment, the solvent is water or a mixture of water with small amounts of co-solvents.
The coating composition used in the practice of the invention may include a catalyst to enhance the cure reaction. For example, when aminoplast compounds, especially monomeric melamines, are used as a curing agent, a strong acid catalyst may be utilized to enhance the cure reaction. Such catalysts are well-known in the art and include, without limitation, p-toluene sulfonic acid, dinonylnaphthalene disulfonic acid, dodecylbenzenesulfonic acid, phenyl acid phosphate, monobutyl maleate, butyl phosphate, and hydroxy phosphate ester. Strong acid catalysts are often blocked, e.g. with an amine. Other catalysts that may be useful in the composition of the invention include Lewis acids, zinc salts, and tin salts.
In a preferred embodiment of the invention, the organic solvent is present in the coating composition in an amount of from 0 weight percent to about 99 weight percent, preferably from 0 weight percent to about 70 weight percent, and more preferably from about 1 weight percent to about 20 weight percent. In a more preferred embodiment, the coating composition is aqueous and includes water in an amount of from about 0.01 weight percent to about 99 weight percent, preferably from about 5 weight percent to about 80 weight percent, and more preferably from about 20 weight percent to about 70 weight percent.
Coating compositions can be coated on the article by any of a number of techniques well-known in the art. These include, for example, spray coating, dip coating, roll coating, curtain coating, and the like. For automotive body panels, spray coating is preferred.
The coating compositions of the invention include electrocoat primer compositions, primer surfacer compositions, and topcoat compositions, including one-layer pigmented topcoat compositions as well as either or both of the clearcoat and basecoat layers of a two-layer topcoat compositions. When the resins of the invention are utilized in aqueous compositions, they may include monomers with groups that can be salted, i.e., acid groups or amine groups. In the case of electrocoat primer compositions, an acid group or amine group is used to deposit the resin on the anode or cathode.
Additional agents, for example surfactants, fillers, stabilizers, wetting agents, dispersing agents, adhesion promoters, UV absorbers, hindered amine light stabilizers, etc. may be incorporated into the coating composition. While such additives are well-known in the prior art, the amount used must be controlled to avoid adversely affecting the coating characteristics. The coating composition according to the invention is preferably utilized in a high-gloss coating and/or as the clearcoat of a composite color-plus-clear coating. High-gloss coatings as used herein are coatings having a 20xc2x0 gloss (ASTM D523-89) or a DOI (ASTM E430-91) of at least 80.
When the coating composition of the invention is used as a high-gloss pigmented paint coating or as a basecoat of a basecoat-clearcoat composite coating, the pigment may be any organic or inorganic compounds or colored materials, fillers, metallic or other inorganic flake materials such as mica or aluminum flake, and other materials of kind that the art normally includes in such coatings. Pigments and other insoluble particulate compounds such as fillers are usually used in the composition in an amount of 1% to 100%, based on the total solid weight of binder components (i.e., a pigment-to-binder ratio of 0.1 to 1).
When the coating composition according to the invention is used as the clearcoat or basecoat of a basecoat-clearcoat composite coating, the composition forming the other layer of the composite coating may any of a number of types well-known in the art, and does not require explanation in detail herein. Polymers known in the art to be useful in clearcoat and basecoat compositions include acrylics, vinyls, polyurethanes, polycarbonates, polyesters, alkyds, and polysiloxanes. Preferred polymers include acrylics and polyurethanes. In one preferred embodiment of the invention, the basecoat composition also utilizes a carbamate-functional acrylic polymer. Basecoat polymers may be thermoplastic, but are preferably crosslinkable and comprise one or more type of crosslinkable functional groups. Such groups include, for example, hydroxy, isocyanate, amine, epoxy, acrylate, vinyl, silane, and acetoacetate groups. These groups may be masked or blocked in such a way so that they are unblocked and available for the crosslinking reaction under the desired curing conditions, generally elevated temperatures. Useful crosslinkable functional groups include hydroxy, epoxy, acid, anhydride, silane, and acetoacetate groups. Preferred crosslinkable functional groups include hydroxy functional groups and amino functional groups.
The coating compositions described herein are preferably subjected to conditions so as to cure the coating layers. Although various methods of curing may be used, heat-curing is preferred. Generally, heat curing is effected by exposing the coated article to elevated temperatures provided primarily by radiative heat sources. Curing temperatures will vary depending on the particular blocking groups used in the cross-linking agents, however they generally range between 90xc2x0 C. and 180xc2x0 C. The first compounds according to the present invention are preferably reactive even at relatively low cure temperatures. Thus, in a preferred embodiment, the cure temperature is preferably between 115xc2x0 C. and 150xc2x0 C., and more preferably at temperatures between 115xc2x0 C. and 140xc2x0 C. for a blocked acid catalyzed system. For an unblocked acid catalyzed system, the cure temperature is preferably between 80xc2x0 C. and 100xc2x0 C. The curing time will vary depending on the particular components used, and physical parameters such as the thickness of the layers, however, typical curing times range from 15 to 60 minutes, and preferably 15-25 minutes for blocked acid catalyzed systems and 10-20 minutes for unblocked acid catalyzed systems.
The invention is further described in the following example. The example is merely illustrative and does not in any way limit the scope of the invention as described and claimed. All parts are parts by weight unless otherwise noted.